Hydrogen-bonding alcohol-water interactions in binary ethanol, 1-propanol, and 2-propanol+methane structure II clathrate hydrates

Saman Alavi, Satoshi Takeya, Ryo Ohmura, Tom K. Woo, John A. Ripmeester

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

The small alcohols ethanol, 1-propanol, and 2-propanol are miscible in water, form strong hydrogen bonds with water molecules, and are usually known as inhibitors for clathrate hydrate formation. However, in the presence of methane or other help gases, clathrate hydrates of these substances have been synthesized. In this work, molecular dynamics simulations are used to characterize guest-host hydrogen bonding, microscopic structures, and guest dynamics of binary structure II clathrate hydrates of methane (small cages) with ethanol, 1-propanol, and 2-propanol in the temperature range of 100-250 K to gain insight into the stability of these materials. We observe that these alcohols form structures with dynamic long-lived (∼10 ps) guest-host hydrogen bonds in the hydrate phases while maintaining the general cage structure of the sII clathrate hydrate form. The hydroxyl groups of ethanol, 1-propanol, and 2-propanol act as both proton acceptors and proton donors and there is a considerable probability of simultaneous hydrogen bonding between O and H hydroxyl atoms with different cage water molecules. The presence of the nonpolar methane molecule and the hydrophobic moieties of the alcohols stabilize the hydrate phase, despite the strong and prevalent alcohol-water hydrogen bonding. The effect of the alcohol molecules on the structural properties of the hydrate and the effect of guest-host hydrogen bonding on the guest dynamics are studied.

Original languageEnglish
Article number074505
JournalJournal of Chemical Physics
Volume133
Issue number7
DOIs
Publication statusPublished - 2010 Aug 21

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1-Propanol
2-Propanol
clathrates
Methane
Hydrates
hydrates
Hydrogen bonds
alcohols
ethyl alcohol
Ethanol
methane
Alcohols
Water
hydrogen
water
Molecules
interactions
Hydroxyl Radical
Protons
molecules

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Hydrogen-bonding alcohol-water interactions in binary ethanol, 1-propanol, and 2-propanol+methane structure II clathrate hydrates. / Alavi, Saman; Takeya, Satoshi; Ohmura, Ryo; Woo, Tom K.; Ripmeester, John A.

In: Journal of Chemical Physics, Vol. 133, No. 7, 074505, 21.08.2010.

Research output: Contribution to journalArticle

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